ISOCYANATE-AMINE-BASED CHEMICAL ANCHOR WITH IMPROVED PERFORMANCE, AND USE THEREOF

Abstract

A multi-component resin system can be used for producing a mortar composition based on isocyanate amine adducts for the chemical fastening of construction elements. A mortar composition based on isocyanate amine adducts can be produced from the multi-component resin system. The mortar composition based on the isocyanate amine adducts is useful for the chemical fastening of construction elements in mineral substrates.

Claims

1: A multi-component resin system, containing: an isocyanate component comprising at least one aliphatic and/or aromatic polyisocyanate having an average NCO functionality of 2 or more, and an amine component comprising at least one amine which is reactive to isocyanate groups and has an average NH functionality of 2 or more, with the proviso that the multi-component resin system is free of polyaspartic acid esters, the isocyanate component and/or the amine component comprising at least one filler and at least one rheology additive, and total filling level of a mortar composition produced by mixing the isocyanate component and the amine component is in a range from 30 to 80 wt. %, wherein the isocyanate component and/or the amine component contains at least one additive, the at least one additive being a compound of formula I
A.sub.n(L).sub.m(X).sub.p(formula I), wherein A is phosphorous, boron, aluminum, titanium, or zirconium, X can be the same or different and is an alkoxy, aryloxy, or acyloxy group, L can be the same or different and is at least one ligand, n is the valency of A, p is an integer from 1 to n, m is 0 or an integer from 1 to n?1, and n=m+p, or a siloxane having at least one functional group which is capable of addition reaction to isocyanates, but which has no hydrolyzable groups bonded to a silicon atom.

2: The multi-component resin system according to claim 1, wherein in the compound of formula I, X is an alkoxy group OR.sup.1 or an acyloxy group O(C?O)R.sup.1, where R.sup.1 is in each case an optionally substituted, linear or branched alkyl group having 1 to 24 carbon atoms.

3: The multi-component resin system according to claim 2, wherein X is a group selected from the group consisting of OCH.sub.3, OC.sub.2H.sub.5, OC.sub.3H.sub.7, OC.sub.4H.sub.9, OC.sub.5H.sub.11, O(CO)CH.sub.3, O(CO)C.sub.2H.sub.5, O(CO)C.sub.3H.sub.7, O(CO)C.sub.4H.sub.9, and O(CO)C.sub.5H.sub.11.

4: The multi-component resin system according to claim 3, wherein X is a group selected from the group consisting of OCH.sub.3, OC.sub.2H.sub.5, OC.sub.3H.sub.7, and OC.sub.4H.sub.9.

5: The multi-component resin system according to claim 1, wherein in the compound of formula I, X is the same.

6: The multi-component resin system according to claim 1, wherein in the compound of formula I, the ligand L is selected from the group consisting of acetoacetate, phosphate, phosphite, sulfate, sulfite, CO, CN, cyclopentyl, and pentamethylcyclopentyl.

7: The multi-component resin system according to claim 1, wherein the compound of formula I is selected from the group consisting of trimethyl phosphate, triethyl phosphate, triethyl borate, triethyl aluminate, triisopropyl borate, tributyl borate, tetraethyl titanate, tetraisopropyl titanate, tetraethyl zirconate, and tetrabutyl zirconate.

8: The multi-component resin system according to claim 1, wherein the compound of formula I is present in an amount of 0.001-10 wt. %, based on a total weight of the multi-component resin system.

9: The multi-component resin system according to claim 1, wherein in the siloxane, the at least one functional group capable of addition reaction with isocyanate groups is a terminal group.

10: The multi-component resin system according to claim 9, wherein the at least one functional group is selected from the group consisting of hydroxy, carboxy, amino, sec, amino, mercapto, isocyanato, alkenyl, (meth)acryloyl, anhydride, and epoxy groups.

11: The multi-component resin system according to claim 1, wherein the siloxane has the structure
R.sub.3Si[OSi(R.sup.1).sub.2].sub.nOSiR.sub.3 wherein n is 0 or an integer from 1 to 1000, inclusive, and R and R.sup.1, independently of one another, are in each case a C.sub.1-C.sub.20-alkyl group or an aralkyl group optionally containing heteroatoms and optionally comprising at least one group capable of addition reaction with isocyanate groups.

12. (canceled)

13: The multi-component resin system according to claim 1, wherein the siloxane is selected from the group consisting of 1,3-bis(2-aminoethylaminoethyl)tetramethyldisiloxane, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, tris(glycidoxypropyldimethylsiloxy)-phenylsilane, 3-methacryloxypropylpentamethyldisiloxane, poly(acryloxypropylmethyl)siloxane, 1,3-bis[(acryloxypropylmethyl)siloxane, 1,3-bis(3-methacryloxypropyl)tetrakis-(trimethylsiloxy)disiloxane, 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane, monomethacryloxypropyl terminated polydimethylsiloxane, poly[dimethylsiloxane-co-(3-(monomethacryloxy)propyl)methylsiloxane], 1,3,-bis(4-methacryloxybutyl)tetramethyldisiloxane, (methacryloxypropyl)methyl siloxane/dimethylsiloxane copolymer, dodecamethylpentasiloxane, 1,1,1,3,5,7,7,7-octamethyl-3,5-bis(trimethylsilanyloxy)tetrasiloxane, trimethylsilyl terminated poly(methylhydro-siloxane), bis(hydroxyalkyl)-terminated poly(dimethylsiloxane), poly[dimethylsiloxane-co-(2-(3,4-epoxycyclohexyl)ethyl)methylsiloxane], diglycidyl ether terminated poly(dimethylsiloxane) poly[dimethylsiloxane-co-[3-(2-(3-hydroxy-ethoxy)ethoxy)propyl]methylsiloxane, and monoglycidyl ether terminated poly(dimethylsiloxane).

14: The multi-component resin system according to claim 1, wherein a proportion of the siloxane is from 0.5 to 20 wt. %, based on a total weight of the multi-component resin system.

15-17. (canceled)

18: The multi-component resin system according to claim 1, wherein the isocyanate component comprises at least one aromatic polyisocyanate selected from the group consisting of 1,4-phenylene diisocyanate, 2,4- and/or 2,6-toluylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthylene diisocyanate, diphenylene methane-2,4- and/or -4,4-diisocyanate, triphenylmethane-4,4,4-triisocyanate, bis- and tris-(isocyanatoalkyl)-benzene, toluene, xylene, and mixtures thereof.

19: The multi-component resin system according to claim 1, wherein the isocyanate component comprises at least one aliphatic polyisocyanate selected from the group consisting of hexamethylene diisocyanate (HDI), trimethyl HDI (TMDI), pentane diisocyanate (PD1), 2-methylpentane-1,5-diisocyanate (MPDI), isophorone diisocyanate (IPDI) 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane (H.sub.6XDI), bis(isocyanatomethyl)norbornane (NBDI), 3(4)-isocyanatomethyl-1-methyl-cyclohexyl isocyanate(IMCI), 4,4-bis(isocyanatocyclohexyl)methane (H.sub.12MDI), and mixtures thereof.

20: The multi-component resin system according to claim 1, wherein the total filling level is in a range from 35 to 65 wt. %, based on a total weight of the multi-component resin system.

21-22. (canceled)

23: A mortar composition, produced by mixing the isocyanate component and the amine component of the multi-component resin system according to claim 1.

24: A method for chemical fastening of a construction element in a borehole, the method comprising: curing the multi-component resin system according to claim 1 in the borehole, to chemically fasten the construction element.

25: A method for improving pull-out values of a chemical anchor, the method comprising: curing the multi-component resin system according to claim 1.

26: The method according to claim 25, wherein the method improves the pull-out strength of the chemical anchor in cleaned boreholes.

Description

EMBODIMENTS

[0147] The following compounds were used to prepare the comparative composition and the composition according to the invention:

TABLE-US-00001 Hexamethylene-1,6-diisocyanate low-viscosity, aliphatic polyisocyanate resin Covestro AG homopolymers based on hexamethylene diisocyanate (equivalent weight approx. 17 NCO content according to M105-ISO 11909 23.5 ? 0.5 wt % according to M10 -ISO 102 3 < 0.25%; viscosity (23? C.) M014-ISO 3219 730 100 mPa .Math. s; Desmodur? N 3900) Mixture of -methyl-2,4- Ethacure? 300 Curative (dimethylthiotoluene Alb Corporation bis(methylthio)phenylene-1,3-diamine and diamine 95-97%, monomethylthiotoluene 2-methyl-4,6-bis(methylthio)phenylene- diamine 2-3%, equivalent weight with 1,3-diamine ( 107) 3-glycidyloxypropyltrimethoxysilane Dynasylan? GLYMO Evonik Resource Efficiancy GmbH Tris(isooctadecanoate-O)(propan-2- Ken-React? KR? TTS FARRL GmbH olato)titanium Hydrogen tetrakis[2,2- Ken-React? KR? 55 FARRL GmbH bis(allyloxy)methyl]butane-1-olato- O bis(ditridecyl phosphilo-O )titanate(2 ) 1,3- ABCR GmbH bis(glycidyloxypropyl)tetramethyldisiloxane Quartz powder Millisil? W12 Quarzwork Silica Cab-O-Sil? TS- 720 Cabot indicates data missing or illegible when filed

[0148] The comparative composition and the compositions according to the invention of the isocyanate component and the amine component are shown in Table 1 below.

TABLE-US-00002 TABLE 1 Compositions of the isocyanate component and the amine component [wt. %] for the comparative example and examples 1 to 4 according to the invention; use of different additives. Comparison Comparison 1 2 1 2 3 Isocyanate Hexamethylene-1,5-diisocyanate 37.5 36 37.5 37.5 36 component homopolymer (Desmodur? N3900) Additive 3-glycidyloxypropyltrimethoxysilane 3 Dynaslan? Glymo Tris(isooctadecancato-O)(propan-2- 0.5 olato)titanium (Ken-React? KR? TTS) Hydrogen tetrakis[2,2- 0.5 bis(allyloxy)methyl]butane-1-olato- O1]bis(ditridecyl phosphito- O )titanate(2-) (Ken-React? KR? 55) 1,3- 3 bis(glycidoxypropyl)tetramethyldisiloxane Quartz powder (W12) 52 50.5 51.5 51.5 50.5 Silica 1.5 1.5 1.5 1.5 1.5 Zeolite (Pumol 3ST Powder) 3 3 3 3 3 Amine (6-methyl-2,4-bis(methylthio)phenylene-1,3- 49.5 49.5 49.5 49.5 49.5 component diamine (2-methyl-4,6- tris(methylthio)phenylene-1,3-diamine (DMTDA) Quartz powder (W12) 49 49 49 49 49 Silica 1.5 1.5 1.5 1.5 1.5 indicates data missing or illegible when filed

[0149] To produce the mortar compositions, the isocyanate component and the amine component were each first produced individually. For this purpose, the constituents indicated in Table 1 were homogenized in a dissolver (PC Laborsystem GmbH, 8 min; 3500 rpm) under vacuum (80 mbar) to form an sir-bubble-tree pasty composition. The isocyanate component and the amine component were then combined with one another and mixed in a speed mixer for 30 seconds at 1500 rpm. The mortar composition obtained in this way was filled into a single-component hard cartridge and injected into a borehole using an extrusion device.

[0150] In order to determine the bond stresses (load values) of the cured fastening compositions, anchor threaded rods Hilti HAS-M12 were inserted into hammer-bored boreholes in C20/25 dry concrete having a diameter of 14 mm and a borehole depth of 72 mm. Here, the boreholes were first cleaned twice with compressed air (6 bar), then twice with a cleaning brush and then again twice with compressed air (6 bar). The boreholes cleaned in this way were then filed halfway with the comparative composition and the compositions according to the invention, and the anchor threaded rods were inserted to an embedding depth of 60 mm. The bond stresses were determined by centrally pulling out the anchor threaded rods. In each case, five anchor threaded rods were inserted and, after 24 hours of curing at approximately 21? C., the bond stress was determined. The fastening compositions were ejected out of the cartridges via a static mixer (HIRT-RE-M mixer; Hilti Aktiengesellschaft) and injected into the boreholes.

[0151] The bond stresses obtained using the mortar formulations described above for dry and well-cleaned boreholes are listed in Table 2 below.

TABLE-US-00003 TABLE 2 Results of the determination of the bond stresses Comparison Comparison 1 2 1 2 3 Bond stress [N/mm.sup.2] 28.8 33.2 31.1 33 32.7

[0152] The results show that the compositions according to the invention have a higher performance in well-cleaned, dry boreholes compared with compositions containing no adhesion promoter. Furthermore, the results show that the claimed additives show comparable values to the silane additives of comparative example 2.